Ink-jet printing apparatus

ABSTRACT

Upon performing printing using a dye ink and a pigment ink and in addition a treatment liquid making those inks insoluble, two kinds of inks consisted of the pigment ink and the dye ink are used. After applying the pigment ink on a printing medium, the dye ink is applied overlaying with the pigment ink. After mixing these inks on the printing medium, the treatment liquid which makes the inks insoluble, is applied. In the alternative, a mixed ink in which a pigment ink not requiring a dispersant and the dye, is used. After application of this mixed ink on the printing medium, the treatment liquid which makes the ink insoluble, is applied. Therefore, problem of “crack”, “soaking out”, “overflow” or lowering of OD value which can be caused upon reaction of the pigment ink and the dye ink or the mixed ink with the treatment liquid, can be solved to achieve high quality printing.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates generally to an ink-jet printing apparatus and a printing method. More particularly, the invention relates to an ink-jet printing apparatus and a printing method performing printing of characters, images and the like on a printing medium, such as a printing paper, an OHP film and the like using an ink and a liquid which makes a coloring material in the ink insoluble (hereinafter also referred to as a treatment liquid).

[0003] 2. Description of the Related Art

[0004] A treatment liquid of this kind reacts with a coloring material contained in an ink, such as a pigment, dye and the like and makes the coloring material insoluble. In the ink-jet printing technology, in general, the treatment liquid is ejected overlaying on the portion where the ink is ejected on the printing medium or in the vicinity thereof, for admixing the ink and the treatment liquid to cause reaction. Then, as a result of reaction, the coloring material if the ink is fixed on the surface of the printing medium or with penetrating into the printing medium for achieving water resistance of the printing product.

[0005] It has also been known that action for making the coloring material in the ink insoluble also serves for limiting penetration of the pigment or dye in a surface layer of the printing medium, to result in improvement of an optical density of the printing medium (hereinafter occasionally simply referred to as “OD value”).

[0006] However, in the conventional ink-jet printing technology using the foregoing treatment liquid, it has been newly recognized by the inventors that there have been respective problems per coloring materials to be employed in the ink for improving printing quality.

[0007] When a dye is used as the coloring material, a first problem is encountered in that sufficiently high OD value cannot be obtained even when the dye and the treatment liquid are reacted. This is because that the dye per se cannot develop relatively low OD value as used for printing. Therefore, even if the treatment liquid and the dye are reacted to fix the most part of the dye in the surface layer of the printing medium as above-mentioned, the OD value is not so high as compared with the case where pigment is used as the coloring material.

[0008] The second problem to be encountered in the dye that the inventor has found, is a phenomenon so-called “overflow” or “sweep”, and particularly that an edge portion of a printed image becomes blur.

[0009]FIGS. 1A to 1D are illustrations for explaining the phenomenon in the predictive manner. As shown in FIG. 1A, when an ink I_(d) using a dye as a color agent, is deposited on the lower penetrative printing medium P such as a plane paper by ejection of the ink through a printing head as an ejecting portion, a part of the ink penetrates into the printing medium and remaining part of the ink is present in a liquid state on the surface of the printing medium P. Then, as shown in FIG. 1B, in the similar manner, a treatment liquid S is deposited overlaying over the ink I_(d) to cause reaction in a boundary between the treatment liquid S and the ink I_(d) by ejection through the printing head. As shown in FIG. 1C, a part of a reaction product flows out to the circumference of the ink I_(d) and flows into the lower side of the ink I_(d). Then, associating with progress of such phenomenon, a reaction between the dye in the ink I_(d) and the treatment liquid S is gradually progressed. Finally, an ink dot consisted of the reaction product of the dye and the treatment liquid is formed as shown in FIG. 1D. The ink dot thus formed has a contour portion where the ink flows over a contour of the dot that should be.

[0010] According to prediction by the inventor, the foregoing phenomenon is caused by flow of a gel form high viscous reaction product in the ink and the treatment liquid for relatively low reaction speed between the dye and the treatment liquid.

[0011] Flowing out of the ink in the ink dot shown in FIG. 1D due to such phenomenon makes the contour blur at the edge portion of an image, and appears as so-called “overflow” to cause degradation of the printing quality. Fluidizing of the foregoing reaction product also causes “sweep” the reaction product in a direction of occurrence of a relative speed between a printing medium fed and the printing head for the treatment liquid. Even therefore, it has been predicted that the edge portion of the printed image becomes blur, similarly.

[0012] The second problem concerning dye set forth above may not cause in the construction where only dye ink is used and the treatment liquid is not used in printing. Accordingly, in the construction where printing is performed using the dye ink and the treatment liquid which makes the dye ink insoluble, particular technical problem is encountered.

[0013] Next, even if printing is performed using an ink including a pigment as the coloring material and the treatment liquid therefor, particular problem caused due to reaction between the ink and the treatment liquid will be explained hereinafter.

[0014] The pigment ink per se exhibits relatively high OD value as used for printing. By reaction with the treatment liquid, owing to the effect of the treatment liquid set forth above, the OD value of the pigment ink can be improved. In comparison with the foregoing dye, the pigment has high reaction speed with the treatment liquid.

[0015] However, as the first program in the case where pigment is used, a problem of “crack” has been found by the inventors. Namely, when reaction of the pigment ink and the treatment liquid is caused especially on the film-like printing medium for an OHP, since reaction speed of the pigment with the treatment liquid is high as set forth above, most part of the pigment coagulated on the surface before penetration into the printing medium. Furthermore, owing to property of the pigment, the pigment may coagulate strongly. Therefore, after once penetrating a solvent in the ink into the printing medium and fixed therein, the coagulated reaction product set forth above will become relatively large individual blocks due to coagulation force to form gaps not filled by the reaction product between these individual blocks. This phenomenon is perceived as “crack” upon observing visually to degrade quality of the printed image. When the foregoing reaction product is not filled, the surface of the printing medium is exposed to lower OD value of the overall printed image.

[0016] In the pigment ink, there are an ink using a dispersant, such as a resin, a surface-active agent and the like, in order to stabilize dispersion of the pigment in the ink solvent (hereinafter occasionally referred to as dispersant containing pigment ink), and an ink using a self-dispersion type pigment and containing no dispersant (hereinafter occasionally referred to as no dispersant containing pigment ink). The second problem concerning the pigment ink is cause in the case where the later no dispersant containing pigment ink and the treatment liquid are used.

[0017] By the inventor, phenomenon called as “soaking out” or “blur” is observed in a dot formed on the printing medium using the no dispersant containing pigment ink and the treatment liquid. FIGS. 2A to 2C are illustrations for predictively explaining this phenomenon.

[0018] After application of the no dispersant containing pigment ink I_(p) on the printing medium P such as a plane paper (see FIG. 2A), the treatment liquid is applied in overlaying manner (see FIG. 2B). Then, production of reaction product is initiated, at first, from the between the ink and the treatment liquid. Then, according to progress of this reaction, radial “soaking out” is caused from substantially circular dot of the reaction product to “blur” the entire circumference of the dot (see FIG. 2C). Such “soaking out” or “blur” appears similar to known feathering. Accordingly, printing quality is lowered.

[0019] The foregoing “soaking out” or “blur” is inferred as the following phenomenon chemically or in micro view. The no dispersant containing pigment ink has relatively high reaction speed in reaction with the treatment liquid. Therefore, the dispersed pigment instantly cause dispersion breakage to generate cluster of the reaction product. In conjunction therewith, particulate reaction product is also generated. Then, the particulate reaction product flows out associating with penetration of the treatment liquid into the printing medium to result in the foregoing “soaking out”.

[0020] As set forth above, in either case of performing printing using the dye ink and the treatment liquid and performing printing using the pigment ink and the treatment ink, there have been problems newly recognized by the inventors, in improving the printing quality, to be solved.

[0021] Associating with respective of the foregoing problems, the applicant of the present invention has proposed use of the ink and the treatment liquid, in which the dye ink and the pigment ink containing the dispersant (Japanese Patent Application Laid-open No. 8-267903). However, the invention disclosed in the above-identified patent application is different from the present invention.

SUMMARY OF THE INVENTION

[0022] The present invention has worked out for solving the technical problems set forth above. It is therefore an object of the present invention to provide an ink-jet printing apparatus and a printing method which can solve or improve respective technical problems to be caused upon printing using a dye ink or a pigment ink and a treatment liquid thereof to enable high quality print.

[0023] Another object of the present invention is to provide an ink-jet printing apparatus and a printing method which can speed up a printing speed upon performing printing using the ink and the treatment liquid.

[0024] In a first aspect of the present invention, there is provided an ink-jet printing apparatus, in which after application of an ink containing a coloring material onto a printing medium, a treatment liquid making the coloring material of the ink insoluble is applied, the ink being a mixed ink, in which a self dispersion type pigment and a dye are mixed, comprising:

[0025] application means for separately applying the mixed ink and the treatment liquid onto the printing medium, for mixing the mixed ink and the treatment liquid in a liquid state on the printing medium.

[0026] In a second aspect of the present invention, there is provided an ink-jet printing apparatus, in which after application of an ink containing a coloring material onto a printing medium, a treatment liquid making the coloring material of the ink insoluble is applied, the ink being a mixed ink, in which a self dispersion type pigment and a dye are mixed, comprising:

[0027] application means for separately applying the mixed ink and the treatment liquid onto the printing medium, for mixing the mixed ink and the treatment liquid in a liquid state on the printing medium, and for mixture of the mixed ink and the treatment liquid, a mixed ink, in which the self dispersion type pigment and the dye are mixed, being further applied on the printing medium in liquid state.

[0028] In a third aspect of the present invention, there is provided an ink-jet printing apparatus employing an ink ejecting portion ejecting an ink and a treatment liquid ejecting portion ejecting a treatment liquid making an ink ejected from the ink ejecting portion insoluble and performing printing by ejecting the treatment liquid after ejection of the ink toward a printing medium, the ink ejecting portion being constituted of at least one mixed ink ejecting portion for ejecting a mixed ink, in which a self dispersion type pigment and dye are mixed, comprising:

[0029] ejecting portion arranging means for arranging the mixed ink ejecting portion and the treatment liquid ejecting portion in a predetermined positional relationship; and

[0030] control means for relatively moving respective ejecting portions arranged in the arranging means and the printing medium, ejecting the mixed ink and the treatment liquid from respective ejecting portions and mixing the mixed ink and the treatment liquid on the printing medium.

[0031] In a fourth aspect of the present invention, there is provided a printing method performing printing by applying a mixed ink, in which a self dispersion type pigment and a dye are mixed, onto a printing medium, and thereafter applying a treatment liquid making the self dispersion type pigment and the dye in the mixed ink insoluble, comprising:

[0032] step of mixing at least the mixed ink and the treatment liquid by applying the mixed ink and the treatment liquid onto the printing medium.

[0033] In a fifth aspect of the present invention, there is provided a printing method performing printing by applying an ink containing a coloring material, and thereafter applying a treatment liquid making the coloring material in the ink insoluble, and the ink being a mixed ink, in which a self dispersion type pigment and a dye are mixed, comprising:

[0034] step of separately applying the mixed ink and the treatment liquid onto the printing medium, mixing the mixed ink and the treatment liquid on the printing medium in liquid state, and, for a mixture of the mixed ink and the treatment liquid, a mixed ink, in which the self dispersion type pigment and dye are mixed, is mixed on the printing medium in liquid state.

[0035] According to the present invention, since the mixed ink and the treatment liquid are mixed on the printing medium, “crack” or “soaking out” which could be caused upon printing by using only the pigment ink and the treatment liquid, can be suppressed by presence of the dye simultaneously mixed. Conversely, lowering of an OD value or “overflow” which could be caused upon printing by using only the dye ink and the treatment liquid, can be compensated, or suppressed by presence of the pigment simultaneously mixed.

[0036] In the present invention, the treatment liquid is effective if the penetration speed is higher than or equal to 5.0 (ml/m²·msec^(1/2)) in Ka value by Bristow method. Thus, in addition to the effect in the case where printing is performed by using the mixed ink and the treatment liquid, since the treatment liquid having relatively high penetration ability as the treatment liquid, the reaction product of the pigment or the like and the treatment liquid may also have high penetration ability to achieve high penetration speed as a whole.

[0037] (First Practical Aspect)

[0038] In a practical aspect of the present invention, the ink using the dye and the pigment with no dispersant as coloring materials (hereinafter referred to as mixed ink) is applied to the printing medium to form a dot of the reaction product by applying the treatment liquid.

[0039]FIGS. 3A to 3C are illustrations for explaining dot formation. As shown in FIG. 3A, at first, the mixed ink I_(m) is applied to the printing medium. Then, as shown in FIG. 3B, the treatment liquid I_(s) is applied overlaying the mixed ink I_(m). Therefore, the reaction product generated by reaction of the mixed ink I_(m) and the treatment liquid S is fixed on the surface and inside of the printing medium P to form the dot.

[0040] According to the practical aspect, firstly, since the ink containing the dye and the pigment without dispersant is used for printing, lowering of OD value to be caused by the dye ink can be compensated by the pigment ink to enhance the OD value. Also, most of the reaction product of the ink as mixed with the treatment liquid may stay in an upper layer of the printing medium to contribute for increasing of the OD value.

[0041] When the ink having low penetration speed as the mixed ink is used, even if an interval to following application of the treatment liquid to provide relatively long period for penetration, the amount of the coloring material staying in the surface layer of the printing medium can be made large to further improve the OD value. In other words, by the effect to be used the ink, in which the dye and the pigment having no dispersant are mixed, the even if the ink having low penetration speed is used, the problem to be caused in using the dye ink and the pigment ink alone can be solved or reduced. By using the ink having further lower penetration speed, increasing of the OD value can be expected. Furthermore, as the effect of using of the ink having low penetration speed, so-called feathering can be suppressed.

[0042] Next, the maximum effect of the practical aspect, in which the treatment liquid is applied after application the mixed ink on the printing medium, is to solve the problem of “overflow” or “sweep” to be caused by the dye ink and the problem of “soaking out” or “blur” to be caused by the pigment ink are solved or reduced simultaneously.

[0043] By the inventors, the principle achieving these effect can be predicted as follow. After application of the mixed ink onto the printing medium, the treatment liquid is applied. Then, the dye and the treatment liquid are reacted to form a gel form high viscous substance. The pigment having no dispersant causes breakage of dispersion by reaction with the treatment liquid. It is considered that fine particle of the pigment generated by dispersion breakage is taken into the high viscous substance of the dye reaction product to restrict “soaking out” or “blur” which could be caused by flowing out of the pigment particle. The high viscous substance taking in the pigment particles has not so high flow ability in comparison with the reaction product of the dye alone and the treatment liquid. Accordingly, occurrence of “overflow” or “sweep” can be suppressed simultaneously. In the construction where the treatment liquid is applied to the mixture of the dye and the pigment having no dispersant, the fine particle of the pigment generated by dispersion breakage are taken in the gel form reaction product so as not to deeply penetrate into the printing medium to bury a gap between fiber of the printing medium in the surface layer. Then, the gel form dye reaction product fills gap between absorbed particles and unevenness of the fiber on the surface of the printing medium. Therefore, irregular reflection of the light can be presented to achieve OD value higher than that achieved when the pigment and the treatment liquid are used.

[0044] According to the practical aspect, as diagrammatically shown in FIG. 3C, phenomenon to be a factor of degradation of the printing quality, such as “blur”, “overflow” or the like, can be prevented. Furthermore, increasing of the OD value can be achieved.

[0045] Phenomenon of “blur” or “overflow” tends to be caused by reaction of the pigment ink or the dye ink with the treatment liquid before penetration into the printing medium. Therefore, in order to suppress occurrence of these phenomena, it becomes necessary to apply the treatment liquid waiting penetration of the dye ink or the like to interfere speeding up of the printing speed. However, in case of the practical aspect, since “blur” or the like can be suppressed by the mixed ink per se, which is a mixture of the dye and the pigment ink having no dispersant, it becomes unnecessary to set the interval for application of the treatment liquid for waiting penetration of the dye ink or the like into the printing medium. Accordingly, speeding up of the printing speed will not be interfered. In other words, the OD value can be further improved by using the mixed ink of the practical aspect having relatively low penetration ability so that the coloring material, such as the pigment or the like may stay in the surface layer of the printing medium for a long period.

[0046] In addition, in the ink-jet printing apparatus employing the full-multi type head, an interval from application of the mixed ink to application of the treatment liquid can be shorted in terms of speeding up, a speed of print for the first one printing medium, called as first print, can be increased. On the other hand, since the foregoing interval can be shortened, down-sizing of the apparatus and lowering of cost can be achieved.

[0047] The order of application of the mixed ink and the treatment liquid onto the printing medium in the practical aspect is basically that the treatment liquid is applied after application of the mixed ink on the printing medium, as set forth above to attain the foregoing effect.

[0048] Concerning particular construction determining order of application, case where a serial type head is used, for example, a plurality of times of scan is performed for the same region with an interval for paper feeding, the foregoing order is realized, respectively, may be encompassed within the scope of the present invention.

[0049] While the mixed ink in the practical aspect is applied in advance of application of the treatment liquid, number of the mixed ink to be applied is not limited to one droplet as set forth above.

[0050] For example, it may be possible to apply two droplets of the mixed ink in advance of application of the treatment liquid. In this case, preferably, among these two droplets, the mixed ink applied at earlier timing is contains greater proportion of dye than the pigment having no dispersant, and the mixed ink applied later timing contains greater proportion of pigment having no dispersant than the dye. Therefore, upon reaction with the treatment liquid applied later, greater proportion of pigment may react with the treatment liquid to further suppress flow out of the reaction product of the dye and the treatment liquid. As another practical aspect which can achieve equivalent effect, number of the mixed ink droplet to be applied in advance of application of the treatment liquid is set to three and proportions of the pigment having no dispersant are preferably increased in the mixed ink to be applied in later timing.

[0051] When a plurality of mixed ink droplets are applied, total amount of the applied ink is set to be substantially equal to the case where one droplet is applied. In other words, according to the practical aspect of the present invention, when the mixed ink is applied with dividing into a plurality of times, even if the amount of the ink becomes smaller according to increasing of number of divided droplets, the foregoing effect can be attained.

[0052] Any difference of timings of application of the mixed ink in the practical aspect and the treatment liquid may be encompassed within the scope of the present invention as long as respective effect of the practical aspect can be achieved, similarly to the order of application set forth above.

[0053] Namely, depending upon a timing from application of the mixed ink to application of the treatment liquid, reaction between the mixed ink and the treatment liquid can be caused in various modes. For example, when the time is short, mixing of the mixed ink and the treatment liquid becomes insufficient. In the circumferential portion of the dot formed by overlaying the mixed ink and the treatment liquid, namely the edge portion, mixing of the pigment or the like and the treatment liquid can be done sufficiently to achieve respective effect of the practical aspect, particularly in suppression of “blur” or “overflow”.

[0054] Therefore, in this disclosure, “mix” of the mixed ink and the treatment liquid means not only wholly mixing but also partial mixing at the edge portion and so on. Furthermore, “mix” also represents mixing after penetration into the printing medium. Modes of all of these mixing will be defined as “mixing in liquid state”.

[0055] Color (kind), density and number of the ink applied in the practical aspect can be combined arbitrary as long as the foregoing order of application is maintained. For example, as the kind of the inks of black (Bk), yellow (Y), magenta (M) and cyan (C) inks are used generally. Concerning respective colors, high and low density inks may also be used. Further particularly, with taking at least one of yellow ink, magenta ink and cyan ink as mixed ink in the practical aspect, and using the treatment liquid, the mixed ink and the treatment liquid are applied in sequential order.

[0056] Among such combinations, for which the present invention is applicable, the most preferred mode is to use the mixed ink as the black ink. According to this mode, respective effect of the practical aspect, such as increasing of the OD value, suppression of “blur” or “overflow” contributes for printing quality of the characters, such as letters or the like.

[0057] As the method applying these mixed ink and so on to the printing medium, various method, such as application or directly contacting the ink or the like to the printing medium for application and so on may be encompassed within the scope of the present invention. The most preferred mode is the ink-jet printing type employing a printing head. Then, in this case, combination and arrangement of the printing head as the ejecting portion is determined according to combination of application order and kinds of the ink including the treatment liquid.

[0058] Particularly, by a construction, in which the heads for the mixed ink and the treatment liquid are arranged in a direction of relative movement of the printing head with respect to the printing medium, the foregoing sequential order of application becomes possible.

[0059] As more particular construction, either case of so-called full-multi type printing head, in which the ink ejection openings are arranged within a range corresponding to the entire width of the printing region in the printing medium or serial type printing head performing movement for scanning relative to the printing medium may permit application of the ink and the treatment liquid.

[0060] In the ink ejection system of the printing head, any known type, such as piezo type or the like can be employed. Most preferred mode is to generate bubble in the ink or the treatment liquid utilizing thermal energy to eject the ink or the treatment liquid by the pressure of the bubble.

[0061] Furthermore, by each printing head, a range where the mixed ink and the treatment liquid are ejected to overlay, is normally controlled per pixel forming the printed image or so on. The foregoing ink or the like are ejected at the same position in overlaying manner. However, application of the present invention is not limited to the foregoing construction. For example, a construction, in which a part of the dot of the mixed ink and the treatment liquid are overlaid to achieve the predetermined effect of the practical aspect or a construction, in which the treatment liquid is applied for data of respective pixels with thinning to cause reaction between the treatment liquid and the pigment or the like flowing from adjacent pixel by bleeding or the like.

[0062] (Second Practical Aspect)

[0063] Another practical aspect of the present invention will be explained.

[0064] The practical aspect is intended to achieve high speed fixing by employing the treatment liquid having high penetration ability as the treatment liquid in the practical aspect.

[0065] High speed fixing is major construction for achieving speeding up of the printing speed, namely for improvement of throughput. By increasing a driving frequency of the printing head or transporting speed of the printing medium, direct improvement of throughput becomes possible. However, when the ink or the like on the printing medium discharged after printing is not yet fixed, inconvenience can be caused in subsequent handling. Also, in a construction where the discharged printing media are stacked, non-fixed ink may cause stain of other printing medium.

[0066] Namely, among various factors contributing for speeding up of the printing speed, factor directly thought of is a discharge speed of the printing medium after completion of printing, which depends on feeding speed of the printing medium or scanning speed of the printing head. Namely, in the printing apparatus employing the full-multi type printing head, the feeding speed of the printing medium in printing operation directly corresponds to the discharge speed. In the printing apparatus employing the serial type printing head, the scanning speed is directly associated with the discharge speed of the printing medium after completion of printing. Then, the feeding speed of the printing medium and so on is correlated to the ink ejection period for the pixel via solution of printing, namely via dot density. Therefore, in the construction performing printing of one pixel by the ink ejected from a plurality of printing head, when the resolution is considered to be fixed, the ejection period and the feeding speed and so on with respect to the pixel is correlated.

[0067] In consideration of respective technical tasks relating to reaction of the dye ink and the pigment ink with the treatment liquid, it is preferred to take a period from ink ejection to ejection of the treatment liquid as long as possible. The reason is that, when the dye ink or the pigment ink reacts with the treatment liquid after penetration into the printing medium, respective of the foregoing phenomenon will be hardly caused. In other words, when printing is performed using the dye ink, the pigment ink and the treatment liquid therefor, the foregoing problem should also interfere speeding up of the printing speed. Particularly, when the dye ink and the pigment ink having low penetration speed is used for achieving improvement of the OD value, problem in interfering speeding up becomes particularly significant.

[0068] In the practical aspect, after application of the mixed ink on the printing medium, by applying the treatment liquid having high penetration speed, respective effect set forth in the first practical aspect can be caused. Even if the mixed ink having relatively low penetration speed is used, the penetration speed is increased associating therewith. Namely, when the penetration speeds of the mixed ink and the treatment liquid with respect to the printing medium are v₁ and v₂ respectively, v₁<v₂ is satisfied. In FIG. 4, phenomenon is shown predictively.

[0069]FIG. 4 shows the case where the mixed ink I_(m) and the treatment liquid S are applied to the printing medium P in the sequential order. In this case, reaction product starts to be generated between the treatment liquid S and the mixed ink I_(m) contacting at the boundary. The penetration speed of the mixture between the treatment liquid S and the mixed ink becomes higher than that of the case where the mixed ink is used alone. Thus, as a whole, by speeding up of the penetration speed to be higher than that in the mixed ink alone, high speed fixing becomes possible.

[0070] In the practical aspect, by using the treatment liquid having high penetration speed, particularly when the mixed ink having low penetration speed is used for improving the OD value or the like, relatively high speed fixing can be achieved.

[0071] (Third Practical Aspect)

[0072] Still further practical aspect of the present invention relates to order of application of the mixed ink and the treatment liquid. Namely, in the practical aspect, after application of the mixed ink, the treatment liquid is applied, and thereafter, the mixed ink is further applied.

[0073] The practical aspect is particularly effective in improvement of OD value, restriction of “overflow”, “blur” or feathering among the foregoing effects. Using the treatment liquid having high penetration ability as the treatment liquid to be applied between application of the mixed ink, relatively high fixing ability can be obtained.

[0074] It is considered that the foregoing function and effect of the practical aspect is achieved for less fluidization be caused in reaction between the initially applied mixed ink and the treatment liquid as relatively small amount of the mixed ink, and when the mixed ink is applied after application of the treatment liquid, since increasing of viscosity due to reaction between the initially applied mixed ink and the treatment liquid is progressed in certain extent and penetration of the ink and so on is also progressed in certain extent to lower flow ability.

[0075] In case of the practical aspect, the ink to be applied after application of the treatment liquid is preferred to be the mixed ink set forth above, but can be a self-dispersion type pigment ink or the dye ink.

[0076] In a sixth aspect of the present invention, there is provided an ink-jet printing apparatus applying a first ink containing a coloring material to a printing medium, applying a treatment liquid for making the coloring material in the first ink insoluble and applying a second ink containing a coloring material, wherein

[0077] the ink includes a pigment ink primarily containing a pigment as the coloring material and a dye ink primarily containing a dye as the coloring material,

[0078] the apparatus comprising applying means for separately applying the pigment ink, the dye ink and the treatment liquid, and, on the printing medium, the pigment ink and the dye ink being mixed with the treatment liquid in liquid state, respectively.

[0079] In a seventh aspect of the present invention, there is provided an ink-jet printing apparatus applying one of a pigment ink containing a pigment as primary coloring material and a dye ink containing a dye as primary coloring material on a printing medium, thereafter applying a treatment liquid making the coloring material in the ink insoluble, and subsequently applying the other of the pigment ink and the dye ink onto the printing medium, comprising:

[0080] applying means for separately applying the pigment ink, the dye ink and the treatment liquid, and, on the printing medium, the pigment ink and the dye ink being mixed with the treatment liquid in liquid state respectively.

[0081] In a eighth aspect of the present invention, there is provided an ink-jet printing apparatus having an ink ejecting portion ejecting an ink containing a coloring material and a treatment liquid ejecting portion ejecting a treatment liquid making a coloring material in the ink insoluble for performing printing by ejecting the treatment liquid after ejecting the ink toward a printing medium, the ink ejecting portion including a dye ejecting portion ejecting a dye ink primarily containing a dye as a coloring material and a pigment ejecting portion ejecting a pigment ink primarily containing a pigment as a coloring material, comprising:

[0082] ejecting portion arranging means for arranging the dye ink ejecting portion, the pigment ink ejecting portion and the treatment liquid ejecting portion in a predetermined positional relationship; and

[0083] control means for relatively moving the ejecting portions arranged by the arranging means and the printing medium, ejecting the pigment ink, the dye ink and the treatment liquid from the ejecting portions, and mixing the pigment ink, the dye ink and the treatment liquid on the printing medium in liquid state.

[0084] In a ninth aspect of the present invention, there is provided an printing method performing printing by applying an ink containing a coloring material, and thereafter applying a treatment liquid making the coloring material in the ink insoluble, and the ink including a pigment ink containing a pigment as a primary coloring material and a dye ink containing a dye as primary color agent, comprising:

[0085] step of separately applying the pigment ink, the dye ink and the treatment liquid onto the printing medium, mixing the pigment ink, the dye ink and the treatment liquid on the printing medium in liquid state, and, at least the pigment ink, the dye ink and the treatment liquid being mixed in liquid state.

[0086] In the present invention, since the pigment ink, the dye ink and the treatment liquid are mixed on the printing medium, “crack” or “soaking out” which could be caused upon printing using the pigment ink and the treatment liquid, can be reduced by the dye ink mixed simultaneously. Conversely, lowering of the OD value or “overflow” which could be caused upon printing using only the dye and the treatment liquid can be compensated or reduced by the pigment simultaneously mixed.

[0087] In the present invention, the treatment liquid is effective when the penetration speed is higher than or equal to 5.0 (ml/m²·msec^(1/2)) in Ka value by Bristow method. Upon printing with mixing the dye ink, the pigment ink and the treatment liquid, in addition to the foregoing function, since the treatment liquid having relatively high penetration ability is used, the reaction product of the pigment ink or the like and the treatment liquid also has high penetration ability to speed up penetration speed as a whole.

[0088] (Fourth Practical Aspect)

[0089] In the practical aspect of the present invention, the dye ink and the pigment ink are mixed on the printing medium, and the treatment liquid is applied to the mixture of the dye ink and the pigment ink to form a dot by the reaction product.

[0090]FIGS. 5A to 5D are illustration for explaining formation of dot. As shown in FIG. 5A, at first, the dye ink I_(d) is applied to the printing medium. Then, as shown in FIG. 5B, the pigment ink I_(p) is applied overlaying the dye ink I_(d). Also, as shown in FIG. 5C, to the liquid, in which the dye ink I_(d) and the pigment ink I_(p) are mixed, the treatment liquid S is applied. Therefore, the reaction product generated by reaction of the mixture liquid of the inks and the treatment liquid S is fixed on the surface and inside of the printing medium P to form the dot, as shown in FIG. 5D.

[0091] According to the practical aspect, at first, the dye ink and the pigment ink are mixed on the printing medium, and mixed ink is used for printing. Therefore, lowering of the OD value caused by printing by the dye ink can be compensated by the pigment to enhance the OD value. Furthermore, the reaction product of the treatment liquid and the mixed ink stays in the upper layer portion of the printing medium in large proportion to increase the OD value.

[0092] When the dye ink and the pigment ink having low penetration speed are used, if the period to application of the treatment liquid is long to provide a long period for penetration, large proportion of the coloring material may stay in the surface layer of the printing medium to enhance the OD value. In other words, by the effect of using of both of the dye ink and the pigment ink explained later, even if the ink having low penetration speed is used, the problems could be caused when the dye ink and the pigment ink are used alone, can be solved or reduced. Therefore, the dye ink or the pigment ink having further lower penetration speed can be used. Thus, further increasing of the OD value can be expected. Furthermore, as a effect of using of the ink having low penetration speed, per se, so-called feathering can be restricted.

[0093] Secondly, in addition to the effect of improvement of the OD value set forth above, as the effect of printing by mixing the dye ink and the pigment ink on the printing medium, the problem of “crack” can be solved or reduced.

[0094] When the printing medium, such as plain paper or the like is used, the dye ink and the pigment ink are mixed on the printing medium, and subsequently, the treatment liquid is applied. The pigment may react with the treatment liquid to coagulate to generate block of the reaction product. In mutual gap between a plurality of blocks thus generated, the reaction product of the dye reacted with the treatment liquid is fluidized to penetrate therein for fill. Therefore, occurrence of so-called “crack” set forth above can be prevented and restricted.

[0095] As the third effect of the practical aspect, in which the dye ink and the pigment ink are mixed on the printing medium and the treatment liquid is applied to the mixed inks, problem of “overflow” or “sweep” could by caused in printing by the dye ink and the problem of “soaking out” or “blur” could be caused upon printing by the pigment ink containing no dispersant can be solved or reduced simultaneously.

[0096] By the inventors, the principle achieving these effect can be predicted as follow. Namely, after application of the mixed ink onto the printing medium, the treatment liquid is applied. Then, the dye and the treatment liquid are reacted to form a gel form high viscous substance. The pigment having no dispersant causes breakage of dispersion by reaction with the treatment liquid. It is considered that fine particle of the pigment generated by dispersion breakage are taken into the high viscous substance of the dye reaction product to restrict “soaking out” or “blur” which could be caused by flowing out of the pigment particles. The high viscous substance absorbing the pigment particle has not so high flow ability in comparison with the reaction product of the dye alone and the treatment liquid. Accordingly, occurrence of “overflow” or “sweep” can be suppressed simultaneously. In the construction where the treatment liquid is applied to the mixture of the dye and the pigment having no dispersant, the fine particles of the pigment generated by dispersion breakage are taken in the gel form reaction product so as not to deeply penetrate into the printing medium to bury a gap between fiber of the printing medium in the surface layer. Then, the gel form dye reaction product fills gap between absorbed particles and unevenness of the fiber on the surface of the printing medium. Therefore, irregular reflection of the light can be presented to achieve OD value higher than that achieved when the pigment and the treatment liquid are used.

[0097] According to the practical aspect, as diagrammatically illustrated in FIG. 5D, in conjunction with restriction of occurrence of phenomenon, such as “blur” or “overflow” which could be factor for degradation of printing quality, effect of increasing of the OD value and “crack” can be achieved as set forth as the foregoing first and second effects.

[0098] The phenomenon of “blur” or “overflow” can be caused by reacting the pigment ink or the dye ink with the treatment liquid before penetration into the printing medium. Therefore, in order to suppress occurrence of these phenomena, it becomes necessary to apply the treatment liquid waiting penetration of the dye ink or the like to interfere speeding up of the printing speed. However, in case of the practical aspect, since “blur” or the like can be suppressed by the mixed ink per se, which is a mixture of the dye and the pigment ink having no dispersant, it becomes unnecessary to set the interval for application of the treatment liquid for waiting penetration of the dye ink or the like into the printing medium. Accordingly, speeding up of the printing speed will not be interfered. In other words, the OD value can be further improved by using the mixed ink of the practical aspect having relatively low penetration ability so that the coloring material, such as the pigment or the like may stay in the surface layer of the printing medium for a long period.

[0099] In addition, in the ink-jet printing apparatus employing the full-multi type head, an interval from application of the mixed ink to application of the treatment liquid can be shorted in terms of speeding up, a speed of print for the first one printing medium, called as first print, can be increased. Since the foregoing interval can be shortened, down-sizing of the apparatus and lowering of cost can be achieved.

[0100] The order of application of the mixed ink and the treatment liquid onto the printing medium in the practical aspect is basically that the treatment liquid is applied after application of the mixed ink on the printing medium, as set forth above to attain the foregoing effect.

[0101] According to study made by the inventors, among the foregoing order of application, it has been appreciated that the sequential order of the pigment ink, the dye ink and the treatment liquid or the sequential order of dye ink, the pigment ink and the treatment liquid are preferred. This is because that the effect of mixing in the practical aspect is most significant when the dye ink and the pigment ink are mixed in certain extent and thereafter reaction is caused with the treatment liquid.

[0102] Among two sequential orders set forth above, when the pigment ink, the dye ink and the treatment liquid are applied in this order, in addition of the effect of the practical aspect set forth above, the effect of restricting so-called strike through can be achieved. Namely, deeper penetration of the coloring material of the dye or the like into the printing medium, so-called strike through that dot formed by this coloring material can be remarkably observed from the back side of the printing medium, can be caused. However, in the sequential order of application set forth above, substantially no strike through can be observed. The reason is supposed that since the pigment applied at earlier timing has relatively large particles in the reaction product with the treatment liquid, the reaction product may be clogged in the gap between the fiber or the like of the printing medium to be impossible to penetrate any further.

[0103] In the sequential order of application of the dye ink, the pigment ink and the treatment liquid, “overflow” or the like which could be caused using the dye ink and the treatment liquid, is hardly caused.

[0104] Any difference of timings of application of the mixed ink in the practical aspect and the treatment liquid may be encompassed within the scope of the present invention as long as respective effect of the practical aspect can be achieved, similarly to the order of application set forth above.

[0105] For example, timing difference of application of the pigment ink and the dye ink can be zero. Namely, the pigment ink and the dye ink may be applied to the printing medium simultaneously. Also, an interval from application of the pigment ink or the like to application of the treatment liquid is desired to include a time for mixing the pigment ink and the dye ink in order to obtain respective effect of the practical aspect set forth above. However, even in a period shorter than the foregoing interval, in the peripheral portion of the dot formed by overlaying the pigment ink and the like, namely the edge portion, sufficient mixing of the pigment and the like can be caused to achieve the effects of the practical aspect. Particularly, at least the effect of suppression of “blur” or “overflow” can be achieved.

[0106] Color (kind), density and number of the ink applied in the practical aspect can be combined arbitrary as long as the foregoing order of application is maintained. For example, as the kind of the inks of black (Bk), yellow (Y), magenta (M) and cyan (C) inks are used generally. Concerning respective colors, high and low density inks may also be used. Further particularly, with taking at least one of yellow ink, magenta ink and cyan ink as mixed ink in the practical aspect, and using the treatment liquid, the mixed ink and the treatment liquid are applied in sequential order.

[0107] Among such combinations, for which the present invention is applicable, the most preferred mode is to use the mixed ink as the black ink. With this mode, respective effect of the practical aspect, such as increasing of the OD value, suppression of “blur” or “overflow” contributes for printing quality of the characters, such as letters or the like.

[0108] In the foregoing explanation, the pigment ink and the dye ink have been explained as those containing only pigment and only dye as coloring material components, respectively, various effects set forth above can be achieved not only by the inks set forth above but also by the pigment ink partly containing the dye or the dye ink partly containing pigment. This the true even for the following explanation. Therefore, in this disclosure, as the coloring material, the ink containing the pigment only or the ink containing the pigment partly containing the dye are defined as “pigment ink containing the pigment as primary coloring material”. Also, the ink containing the dye only or the ink containing the dye partly containing the pigment are defined as “dye ink containing the dye as primary coloring material”.

[0109] As the method applying these mixed ink and so on to the printing medium, various method, such as application or directly contacting the ink or the like to the printing medium for application and so on may be encompassed within the scope of the present invention. The most preferred mode is the ink-jet printing type employing a printing head. Then, in this case, combination and arrangement of the printing head as the ejecting portion is determined according to combination of application order and kinds of the ink including the treatment liquid.

[0110] Particularly, by a construction, in which the heads for the mixed ink and the treatment liquid are arranged in a direction of relative movement of the printing head with respect to the printing medium, the foregoing sequential order of application becomes possible.

[0111] Furthermore, by each printing head, a range where the pigment ink, the dye ink and the treatment liquid are ejected to overlay, is normally controlled per pixel forming the printed image or so on. The foregoing ink or the like are ejected at the same position in overlaying manner. However, application of the present invention is not limited to the foregoing construction. For example, a construction, in which a part of the dot of the pigment ink, the dye ink and the treatment liquid are overlaid to achieve the predetermined effect of the practical aspect or a construction, in which the treatment liquid is applied for data of respective pixels with thinning to cause reaction between the treatment liquid and the pigment or the like flowing from adjacent pixel by bleeding or the like.

[0112] (Fifth Practical Aspect)

[0113] In the practical aspect, applying the treatment liquid having high penetration speed after application of the dye ink and the pigment ink onto the printing medium, the effect explained in the fourth practical aspect can be achieved. Also, even if the dye ink and the pigment ink having relatively low penetration speed is used, penetration speed can be made higher. Namely, penetration speeds of the pigment ink, the dye ink and the treatment liquid relative to the printing medium being v₁<v₃ and v₂<v₃ assuming that the penetration speed of the pigment ink is v₁, the penetration speed of the dye ink is v₂ and the penetration speed of the treatment liquid is V₃.

[0114]FIG. 6 shows the case where the pigment ink I_(p), the dye ink I_(d) and the treatment liquid S are applied on the printing medium P in the sequential order, and shows a condition where the treatment liquid S is applied at a timing-where the pigment ink I_(p) and the dye ink I_(d) are not mixed sufficiently. In this case, the reaction product is generated at the boundary where the treatment liquid S and the dye ink I_(d) contact. At first, since the penetration speed of the treatment liquid S is high, the reaction product may penetrate at high speed than that when the dye ink is used alone. Since reaction between the dye and the treatment liquid per se is relatively low, the treatment liquid S further penetrates during reaction to also react with the pigment ink I_(p) to make the penetration speed of the reaction product higher. Thus, as a whole, speed can be higher than the penetration speed of the case where the pigment ink and the dye ink are used alone to permit high speed fixing.

[0115] In the practical aspect, by using the treatment liquid having high penetration speed, even if the pigment ink and the dye ink having low penetration speed is used for improvement of the OD value and so on, fixing at relatively high speed becomes possible.

[0116] (Sixth Practical Aspect)

[0117] Further practical aspect of the present invention concerns order of application of one of the pigment ink, the dye ink and the treatment liquid. Namely, after application of the dye ink or the pigment ink, the treatment liquid is applied, and subsequently, the other of the pigment ink and the dye ink is applied. More particularly, application is performed in the order of the dye ink, the treatment liquid and then the pigment ink, or in the order of the pigment ink, the treatment ink and then the dye ink.

[0118] According to this practical aspect, in comparison with the practical aspect, in which the treatment liquid is applied after application of both of the pigment ink and the dye ink, flow ability of the reaction product generated by reaction between the ink and the treatment liquid becomes lower to be advantageous in prevention of “overflow” and “sweep”.

[0119] According to the present invention, since the pigment ink, the dye ink and the treatment liquid are mixed on the printing medium, “crack” or “soaking out” which could be caused when printing is performed only by the pigment ink and the treatment liquid can be reduced by presence of the dye ink simultaneously mixed. Conversely, lowering of the OD value or “overflow” which could be caused when printing is performed only by the dye and the treatment liquid, can be compensated by presence of the pigment ink simultaneously mixed and thus can be reduced.

[0120] As a result, high quality printing can be performed with high OD value and avoiding “crack”, “soaking out”, “overflow” and so on.

[0121] In addition to the effect to be achieved by printing with mixing the pigment ink and the treatment liquid, since the treatment liquid having relatively high penetration ability is used, the reaction product of the pigment ink and the treatment liquid may have high penetration ability to make the penetration speed high as a whole.

[0122] As a result, fixing speed can be made higher to enable high speed printing.

[0123] The above and other objects, effects, features and advantages of the present invention will become more apparent from the following description of the embodiments thereof taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0124]FIGS. 1A to 1D are illustrations for predictively explaining “overflow” phenomenon of reaction product upon reaction of a dye ink and a treatment liquid therefor;

[0125]FIGS. 2A to 2C are illustrations for predictively explaining “soaking out” phenomenon of reaction product upon reaction of a pigment ink and a treatment liquid therefor;

[0126]FIGS. 3A to 3C are illustrations for predictively explaining dot formation upon reaction with the treatment liquid after application of an ink, in which both of a no dispersant containing pigment and a dye are mixed, in one practical aspect of the present invention;

[0127]FIG. 4 is an illustration for explaining reaction and penetration with a mixed ink when a high penetrative treatment liquid is used as the treatment liquid in another practical aspect of the present invention;

[0128]FIGS. 5A to 5D are illustrations for predictively explaining reaction with the treatment liquid after mixing of the pigment ink and the dye ink on the printing medium in other practical aspect of the present invention;

[0129]FIG. 6 is an illustration for explaining reaction and penetration with the pigment ink and the dye ink when high penetrative treatment liquid is used as the treatment liquid, in a further practical aspect of the present invention;

[0130]FIG. 7 is a side elevation showing a general construction of one embodiment of a printing apparatus according to the present invention;

[0131]FIG. 8 is a block diagram showing a construction of a control system of the printing apparatus shown in FIG. 7;

[0132]FIG. 9 is a diagrammatic illustration showing a relationship between acetylenol content and a Ka value indicative of a penetration speed;

[0133]FIGS. 10A and 10B are characteristic charts each showing relationship between ink penetration amount and elapsed period;

[0134]FIG. 11 is a perspective view showing a construction of another embodiment of the printing apparatus according to the present invention;

[0135]FIGS. 12A to 12C are diagrammatic illustration showing a head construction of a further embodiment of the printing apparatus according to the present invention;

[0136]FIG. 13 is a perspective view showing a construction of a still further embodiment of the printing apparatus according to the present invention;

[0137]FIGS. 14A to 14C are graphs showing relationship between a ratio of pigment and printing ability;

[0138]FIGS. 15A to 15D are diagrammatic illustration showing respective of anionic self-dispersion type pigment, anionic dye, cationic surface active agent, cationic high polymer;

[0139]FIG. 16 is a diagrammatic illustration showing reaction mode at a boundary portion between tow anionic self-dispersion type pigment intervening cationic high polymer;

[0140]FIG. 17 is a diagrammatic illustration-showing reaction mode at a boundary portion between two anionic self-dispersion type pigment intervening anionic dye and cationic high polymer; and

[0141]FIG. 18 is a diagrammatic illustration showing reaction mode at a boundary portion between two anionic self-dispersion type pigment intervening anionic dye, cationic surface active agent and cationic high polymer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0142] Particular embodiments of the foregoing practical aspects will be explained hereinafter with reference to the drawings.

[0143] (First Embodiment)

[0144]FIG. 7 is a side elevation showing a general construction of one embodiment of a full-line type printing apparatus according to the present invention.

[0145] A shown printing apparatus 1 employs an ink-jet printing type performing printing by ejecting an ink and a treatment liquid by a plurality of full-line type printing heads as an ejecting portion arranged at predetermined positions along a feeding direction of a printing medium (a direction of arrow A in FIG. 1). The shown printing apparatus 1 is operated under control by a control circuit shown in FIG. 8, which will be explained later.

[0146] Respective printing heads 101Bk1, 101Bk2, 101S, 101C, 101M and 101Y of a head group 101 g can perform printing for a printing paper of maximum A3 size by arranging about 7200 ink ejection openings in a width direction (perpendicular direction of the paper surface of FIG. 7) of the printing paper fed in the direction A in FIG. 7.

[0147] The printing paper 103 is fed in the direction A by rotation of a pair of registration rollers 114 which are driven by a motor for feeding. Then, a tip end of the printing paper 103 is registered as guided by a pair of guide plates 115. Thereafter, the printing paper 103 is fed by a feeding belt 111. The feeding belt 111 as an endless belt is held by two rollers 112 and 113. Deflection of the upper side portion of the feeding belt 111 in vertical direction is restricted by a platen 104. By driving the roller 113 for rotation, the printing paper 103 is fed. Suction of the printing paper 103 onto the feeding belt 111 is performed by electrostatic suction. The roller 113 is driven to rotate by a driving source, such as a motor for rotation to feed the printing paper 103 in the direction of arrow A. While the printing paper 103 is fed on the feeding belt 111, the printing paper 103 printed by the printing head group 101 g is ejected on a stacker 116.

[0148] Each printing head of the printing head group 101 g is consisted of two heads 101Bk1 and 101Bk2 ejecting the mixture ink of black color as set forth in the foregoing practical aspect, a head 101S for a treatment liquid ejecting the treatment liquid, heads for color inks (cyan head 101C, magenta head 101M, yellow head 101Y), arranged as shown along the feeding direction A of the printing paper 102. Then, by ejecting the respective ink and the treatment liquid through the printing head, character of black or color image can be printed.

[0149]FIG. 8 is a block diagram showing a construction of a control system in the full-line type printing apparatus 1 shown in FIG. 7.

[0150] A system controller 201 has a microprocessor, ROM storing a control program to be executed by the shown apparatus, RAM to be used as a work area performing a process of the microprocessor, and so on, for performing control of the overall apparatus. A motor 204 is controlled driving thereof via a driver 202 and driven to rotate the roller 113 shown in FIG. 7 to feed the printing paper.

[0151] A host computer 206 transports information to be printed for this embodiment of the printing apparatus 1 to control printing operation. A reception buffer 207 temporarily stores data from the host computer 206 for accumulating data until data is read in by the system controller 201. A frame memory 208 is memories for developing data to be printed into the image data and has a memory size necessary for printing. In this embodiment given hereinafter that the frame memory 208 is designed for storing one printing paper. However, the present invention should not be limited by memory capacity.

[0152] The buffers 209S and 209P temporarily stores data to be printed and varies storage capacity depending upon number of ejection openings of the printing head. A print control portion 210 is designed for appropriately control driving of the printing head by a command from the system controller 201, for controlling a driving frequency, a numbers of printing data and so on. The print control portion 210 also makes data for ejecting the treatment liquid. A driver 211 performs driving of the printing head 101S for ejecting the treatment liquid, printing heads 101BK1, 101Bk2, 101C, 101M and 101Y for respectively ejecting ink, and is controlled by a signal from the print control portion 210.

[0153] The print data from the host computer 206 is transferred to and temporarily stored in the reception buffer 207. Next, the stored print data is read out by the system controller 201 and is developed in the buffers 209S and 209P. Plugging, consuming out of the ink, out of paper and so on can be detected by various detection signal from an abnormality detecting sensor 222.

[0154] The print control portion 210 performs generation of data for treatment liquid in order to eject the treatment liquid on the basis of the image data developed in the buffers 209S and 209P. Then, on the basis of the print data and the treatment liquid data in respective buffers 209S and 209P, ejection operation of respective printing head is controlled.

[0155] In the shown embodiment, concerning mixed ink of black ejected from the heads 101Bk1 and 101Bk2, an ink having low penetration speed (hereinafter referred to as low penetrative ink) is used. The treatment liquid and respective inks of cyan, magenta and yellow to be ejected through respective printing heads 101S, 101C, 101M and 101Y are the treatment liquid and the inks having high penetration speed (hereinafter referred to as high penetrative ink in the this embodiment).

[0156] Here, penetration speed will be briefly explained hereinafter.

[0157] Expressing penetration ability of the ink by an ink amount V per 1 m², for example, it has been known that an ink penetration amount (unit: ml/m²=μm) in a period t from ejection of the ink droplet is expressed by the following Bristow formula:

V=Vr+Ka(t−tw)^(1/2)

[0158] wherein Lt>tw

[0159] Immediately after deposition of the ink droplet on the surface of the printing paper, the ink droplet is mostly accommodated in uneven portion of the surface of the printing paper, namely roughness portion of the surface of the printing paper and little amount of the ink is penetrated into the printing paper. This period is a period tw (contact time) and an accommodated amount to be accommodated in the uneven portion of the surface of the printing paper is indicated by character Vr. When the elapsed time after deposition of the ink droplet onto the surface of the printing paper exceeds the wet time tw, the penetration amount V is increased in an amount proportional to (½)th power of the exceeding period (t−tw). Ka is a proportional coefficient of increased component and becomes a value corresponding to the penetration speed.

[0160]FIG. 9 is an illustration showing a value of the proportional coefficient Ka with respect to a content of ethylene oxide-2,4,7,9-tetramethyl-5-decyne-4,7-diol (hereinafter referred to as acetylenol: tradename, available from Kawaken Fine Chemical) in the ink, obtained through experiments.

[0161] Ka value was measured by means of a dynamic penetration testing device S (made by Toyo Seiki Seisakusho). In this experiments, a PB paper (tradename) as a plane paper available from Canon Kabushiki Kaisha as applicant of the present invention has been used. The PB paper is a printing paper to be used in an electrophotographic type copy machine, a laser beam printer (LBP) and an ink-jet printing type printer.

[0162] Also, for a PPC sheet as a paper for electrophotography available from Canon Kabushiki Kaisha, similar result could be obtained.

[0163] A curve shown in FIG. 9 is a curve increasing Ka value (vertical axis) according to increasing of acetylenol content (horizontal axis). As can be appreciated from this, the proportional coefficient Ka is determined depending upon content of acetylenol. Therefore, penetration speed of the ink is determined substantially depending upon the content of the acetylenol. Lines parallel to the vertical axis and intersecting with the curve represent ranges of fluctuation of the measurement result.

[0164]FIGS. 10A and 10B are characteristic charts showing a relationship between the ink penetration amount and the elapsed time, in which are shown results of experiments performed using a printing paper of 64 g/m², of thickness about 80 μm and of void fraction about 50%.

[0165] In FIG. 10A, the horizontal axis represents (½)th power of the elapsed time t (msec^(1/2)), and in FIG. 10B, the horizontal axis represents the elapsed time t (msec). In both figures, the vertical axes represent penetration amount V (μm). In FIGS. 10A and 10B, curves of the cases of acetylenol contents of 0%, 0.35% and 1% are shown, respectively.

[0166] As can be clear from FIGS. 10A and 10B, the penetration amount of the ink relative to the elapsed period becomes greater at greater content of the acetylenol. In the graphs shown in FIGS. 10A and 10B, there are illustrated tendencies that the wet time tw becomes shorter at greater content of acetylenol and ink penetration ability becomes higher at greater content of acetylenol.

[0167] When acetylenol is not mixed in an ink, namely acetylenol content is 0%, ink penetration ability is low to have a property as low penetrative ink which will be defined later. When acetylenol is mixed in the content of 1%, the ink has a property to be penetrated into the printing paper in a short period, and has a property as high penetrative ink. Then, the ink, in which acetylenol is mixed in the content of 0.35%, has a property of semi-penetrative ink between the low penetrative ink and the high penetrative ink.

[0168] Properties of the foregoing low penetrative ink, the high penetrative ink and the semi-penetrative ink therebetween are shown in the following table 1. TABLE 1 Ka Value Acetylenol Surface Tension (ml/m² · msec^(1/2)) Content (%) (dyne/cm) Low penetrative <1.0 <0.2 40≦ ink Semi-Penetrative 1.0 ≦ <5.0 0.2 ≦ <0.7 35 ≦ <40 Ink High Penetrative 5.0≦ 0.7≦ <35 Ink

[0169] The foregoing table 1 shows Ka value, acetylenol content (%) and surface tension (dyne/cm) of respective low penetrative ink, the semi-penetrative ink and high penetrative ink, respectively. The penetration ability of respective ink for the printing paper as the printing medium becomes higher at greater Ka value. Namely, the penetration ability of the ink becomes higher at smaller surface tension.

[0170] In the table 1, the Ka value has been measured by the dynamic penetration test device S (made by Toyo Seiki Seisakusho) of the liquid by the foregoing Bristow method). In the experiments, the PB paper available from Canon Kabushiki Kaisha as applicant of the present invention has been used. Also, for the PPC paper as a paper for electrophotography available from Canon Kabushiki Kaisha, similar result could be obtained.

[0171] Here, as a condition in the case where the surface-active agent is contained in certain liquid, it has been known that there is a critical micell concentration (CMC) of the surface-active agent in the liquid. The critical micell concentration represents a concentration when a concentration of a solution of the surface-active agent is elevated abruptly causing gathering of several tens molecules to form a micell. Acetylenol contained for adjustment of penetration of the ink set forth above is a kind of surface-active agent. Even in acetylenol, the critical micell concentration is present depending upon the liquid.

[0172] As a relationship with the surface tension in the case where acetylenol content is adjusted, there is a relationship that when micell is formed, the surface tension may not be lowered. Then, it has been confirmed that CMC of acetylenol with respect to water is about 0.7%.

[0173] Making the critical micell concentration shown in FIGS. 10A and 10B corresponded to the foregoing table 1, for example, the high penetrative ink defined in the foregoing table 1 is appreciated as the ink containing acetylenol at a higher content than that of CMC of acetylenol in water.

[0174] Compositions of the treatment liquid and respective inks to be used in this embodiment are as follows: [Treatment Liquid] glycerin 7 Wt. % diethylene glycol 5 Wt. % acetylenol EH 0.7 Wt. % (made by Kawaken Fine Chemical) polyarylamine 4 Wt. % (molecular weight: 1500 and less, medium molecular weight: about 1000) ethanoic acid 4 Wt. % Benzalkonium chloride 0.5 Wt. % triethylene glycol monobutylether 3 Wt. % water remainder [Yellow (Y) Ink] C. I. direct yellow 86 3 Wt. % glycerin 5 Wt. % diethylene glycol 5 Wt. % acetylenol EH 1 Wt. % (made by Kawaken Fine Chemical) water remainder [Magenta (M) Ink] C. I. direct acid red 289 3 Wt. % glycerin 5 Wt. % diethylene glycol 5 Wt. % acetylenol EH 1 Wt. % (made by Kawaken Fine Chemical) water remainder [Cyan (C) Ink] C. I. direct blue 199 3 Wt. % glycerin 5 wt. % diethylene glycol 5 Wt. % acetylenol EH 1 Wt. % (Kawaken Fine Chemical) water remainder [Mixed Ink of Black (Bk)] pigment dispersion liquid 25 Wt. % food black 2 2 Wt. % glycerin 6 Wt. % trietylene glycol 5 Wt. % acetylenol EH 0.1 Wt. % (made by Kawaken Fine Chemical) water remainder

[0175] The Ka value of this mixed ink of black is 0.33. The above pigment dispersion liquid is as follow.

[0176] [Pigment Dispersion Liquid]

[0177] In a solution prepared by mixing 5 g of concentrated hydrochloric acid in 5.3 g of water, 1.58 g of anthranilic acid was added at a temperature of 5° C. The solution was stirred in an ice bath to be constantly maintained at a temperature lower than or equal to 10° C. Then, a solution prepared by dissolving 1.78 g of Fantrium nitrile in 8.7 g of water at a temperature of 5° C., was added. Furthermore, after stirring for 15 minutes, 20 g of carbon black having surface area of 320 m²/g and DBP oil absorption of 120 ml/100 g is added in the mixed condition. Then, further stirring was performed for 15 minutes. Obtained slurry was filtered by Toyo Roshi No. 2 (made by Advantice Co.). Then, pigment particle was washed sufficiently and dried in an oven at a temperature of 110° C. Thereafter, by adding water to the pigment, a pigment solution having a pigment concentration of 10 Wt. % was prepared. Therefore, a pigment dispersion liquid, in which self-dispersion type carbon black charged to have anion property and coupled with hydrophilic radical via a phenyl radical on the surface, as expressed by the following chemical formula:

[0178] As can be clear from respective composition set forth above, depending upon content of acetylenol, the pigment ink and the dye ink of black are set as low penetrative ink and the treatment liquid and respective inks of C, M, Y are set as high penetrative ink, respectively.

[0179] Concerning the pigment ink of black, as explained in the foregoing practical aspect, the pigment ink, not using the dispersant, namely, no dispersant pigment ink, is used. In this ink, as anionic carbon black dispersing element, self-dispersion type carbon black dispersing element, in which at least one kind of hydrophilic radical is coupled on the surface of the carbon black directly or via other atomic group, is preferred for use. As self-dispersion type carbon black, one having ionicity is preferred, and one charged to have anionic property is preferred.

[0180] When carbon black is charged to have anionic property, the hydrophilic radical to be coupled with the surface of carbon black may be —COOM, —SO₃M, —PO₃HM, —PO₃M₂, —SO₂NH₂, —SO₂NHCOR and so on (wherein M represents one of hydrogen atom, alkali metal, ammonium and organic ammonium, R represents alkyl radical having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl radical which may have substituent group), for example. In this embodiment, it is especially preferred to use those charged to have anionic property with coupling —COOM or —SO₃M on the surface of carbon black.

[0181] “M” in the hydrophilic radical may be alkali metal such as lithium, sodium, potassium or the like. Alternatively, the hydrophilic radical may be organic ammonium such as mono-, di-, or tri-methyl ammonium, mono to triethyl ammonium, or mono-, di-, or tri-methanol ammonium. As a method for obtaining carbon black charged to have anionic property, such as for linking —COONa on the surface of carbon black, for example, a method for oxidizing carbon black with hydrochlorite soda can be considered. Of course, the present invention is not limited to these.

[0182] In this embodiment, it is preferred to use carbon black, on the surface of which hydrophilic radical is coupled with other atom group. As other atom group, alkyl group having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl which may have substituent group may be used. In addition to the foregoing example, —C₂H₄COOM, —PhSO₃M, or —PhCOOM and so on (wherein Ph represents phenyl radical) may be used. However, as a matter of course, the present invention is not limited to those exemplified above.

[0183] Carbon black, to the surface of which the anionic radical set forth above is bound directly or via other atom group may be prepared by the following method, for example.

[0184] Namely, as a method for introducing —COONa radical on the surface of carbon black, a method of performing oxidation process for commercially available carbon black with hydrochlorite soda, for example, may be used. On the other hand, for example, as a method for binding —Ar—COONa radical (wherein Ar represents aryl radical) on the surface of carbon black, a method to bind diazonium prepared by acting nitrous acid to NH₂—Ar—COONa radical on the surface of the carbon black, may be used. However, as a matter of course, the present invention should not be limited to these method.

[0185] The self-dispersion type pigment to be contained in the ink of this embodiment is preferred that 80% or more of the particle thereof have particle size within a range of 0.05 to 0.3 μm, more particularly within a range of 0.1 to 0.25 μm. A method of preparation of such ink is as explained in the foregoing embodiment.

[0186] Carbon black in the no dispersant pigment ink per se does not require addition of pigment dispersion resin or surface-active agent to attain superior water dispersion ability in comparison with the conventional carbon black. Therefore, in comparison with the conventional pigment ink, carbon black set forth above is advantageous in higher fixing ability, higher wetting ability and so on. Thus, such carbon black is superior in reliability as used in the printing head.

[0187] By using the mixture ink of black in this embodiment, for a liquid, in which carbon particulate and black dye charged at the same polarity are mixed and dispersed, the treatment liquid containing different polarity of high molecular is reacted.

[0188] In this embodiment, the ink ejection openings in each printing head are arrayed in a density of 600 dpi. In the feeding direction of the printing paper, printing is performed at a dot density of 600 dpi in the feeding direction of the printing paper. Therefore, the dot density of the image or the like to be printed in the embodiment is 600 dpi in both of row direction and column direction. Ejection frequency of respective dot is 4 KHz. Accordingly, a feeding speed of the printing paper becomes about 170 mm/sec. Furthermore, a distance D_(i) between the heads 101Bk1 and 101Bk2 of the mixed ink and the treatment liquid of the head 101S (see FIG. 7) is 80 mm. Accordingly, a period from ejection of the pigment ink of black to ejection of the treatment liquid becomes about 0.48 sec. The ejection amount of each printing head is 15 pl per one ejection. Even when an interval from ejection of the black ink Bk to ejection of the treatment liquid S is set at 0.1 seconds, substantially similar result of evaluation could be obtained.

[0189] Next, for effect and comparison concerning printing quality and so on upon performing printing for a predetermined image of black by this embodiment, explanation will be given using the following tables 2 and 3. TABLE 2 Evaluation Comparative Comparative Item System Embodiment Example 1 Example 2 OD Average OD 1.50 1.40 1.37 Value Value of Among Six Printing Papers Minimum OD 1.45 1.29 1.34 Value of Among Six Printing Papers Effective Timing of Water Immediately Within 48 Immediately Resistance After Hours After Printing Printing Fixing Ability Within About About (Minimum Among Six 10 Sec. 80 Sec. 90 Sec. Printing Papers)

[0190] In the foregoing table 2, similarly this embodiment, both comparative examples show the case where the same predetermined image is printed at resolution of 600 dpi. The first comparative example 1 is a system employing only one head ejecting the pigment ink in an amount of 30 pl per one ejection and not using the treatment liquid, and the second comparative example 2 is a system using a head ejecting a dye ink of black in an amount of 30 pl per one ejection and a head ejecting the treatment liquid having relatively low penetration in an amount of 15 pl per one ejection. The embodiment and the comparative examples in the foregoing table 2 perform printing of the predetermined image on mutually different 6 kinds of printing papers and the table 2 shows the results of measurement of OD value and so on. Among evaluation items shown in the table 2, the OD value is measured using a Machbeth density measuring device. A timing, at which water resistance becomes effective, is not a timing where disturbance of image is hardly recognized when water is dripped after printing. Also, a fixing ability is a timing where set off is not caused upon discharging of the printed product.

[0191] As can be clear from the table 2, in case where the system shown in this embodiment, the system is particularly superior in OD value and fixing ability. TABLE 3 Comparative Comparative Embodiment Example 3 Example 4 Evaluation (Mix) + (Pigment) + (Dye) + Item System (Mix) (Pigment) (Dye) OD Average OD 1.50 1.40 1.38 Value Value of Six Printing Papers Minimum OD 1.45 1.37 1.34 Value of Six Printing Papers Fixing Ability ◯ ◯ ◯ Restric- Period of Bk → S ◯ X X tion of 0.48 sec. Feathering Period of Bk → S ◯ X X (Blur or  1.9 sec. the like) Sharpness Period of Bk → S ◯ X X of Edge of 0.48 sec. Solid Period of Bk → S ◯ X X Printing  1.9 sec.

[0192] In this embodiment of the apparatus shown in FIG. 7, both of the black inks ejected from the heads 101Bk1 and 101Bk2 for black ink were the pigment inks in the case of the comparative example 3 and the dye inks in the case of the comparative example 4.

[0193] It can be appreciated that the embodiment exhibits superior OD value. Namely, concerning this OD value, in this embodiment where the treatment liquid is applied for the ink, in which the pigment requiring no dispersant and dye are mixed, the foregoing effect achieved by mixing of the pigment ink and the dye ink to obtain higher OD value than the case where the treatment liquid is applied to only pigment or only dye.

[0194] When comparison is made in terms of suppression of feathering (“blur” or “soaking out”) or restriction of lowering of sharpness (restriction of “overflow”), the embodiment exhibits superior effect than the comparative examples.

[0195] Even when an interval from ejection of the black ink Bk to ejection of the treatment liquid S in table 3 is set as 0.1 seconds, substantially similar result of evaluation could be obtained.

[0196] The full-multi type printing apparatus described above is used in a condition where the printing head is fixed during printing operation. Therefore, a period required for feeding the printing paper substantially correspond a period required for printing. Thus, the present invention is suitable for high speed printing. Accordingly, by application of the present invention to the high speed printing apparatus, high speed printing function can be further improved. Furthermore, in view of the OD value and restriction of “soaking out”, “overflow” and so on, high quality printing can be achieved.

[0197] While the embodiment of the printing apparatus is employed in a printer in the most typical case, the application is not limited to this but can be constructed as a printing portion of copy machine, facsimile and so on.

[0198] The effect of the embodiment explained with reference to tables 2 and 3 is not limited to the construction employing two heads with respect to black mixed ink but can be a construction employing a single head with ejection amount of 30 pl.

[0199] (Second Embodiment)

[0200]FIG. 11 is a general perspective view showing a construction of the second embodiment of a serial type printing apparatus 5 according to the present invention. Namely, the printing apparatus which ejects the treatment liquid after application of the mixed ink on the printing medium for causing reaction, is not limited to the full-line type but can be a serial type apparatus. Similar elements to those illustrated in FIG. 7 will be identified by like reference numerals to neglect detailed description thereof in order to avoid redundant disclosure to keep the disclosure simple enough to facilitate clear understanding of the present invention.

[0201] The printing paper 103 as the printing medium is inserted from a paper feeding portion 105 and discharged through a printing portion 126. In the embodiment, generally widely used inexpensive plain paper is used as the printing paper 103. In the printing portion 126, the carriage 107 is constructed to mount the printing heads 101Bk, 101S, 101C, 101M and 101Y and to move reciprocally along the guide rail 109 by a driving force of the not shown motor. The printing head 101Bk ejects the mixed ink of black discussed in the former embodiment. On the other hand, the printing heads 101S, 101C, 101M and 101Y respectively ejects the treatment liquid, cyan ink, magenta ink and yellow ink and are driven in sequential order for ejecting the treatment liquid and inks.

[0202] To respective heads, the ink and the treatment liquid are supplied from respectively corresponding ink tanks 108Bk, 108S, 108C, 108M and 108Y. Upon ink ejection, drive signals are supplied to electrothermal transducers, namely heaters, provided for respective of the ejection openings of respective heads to thereby apply thermal energy to the ink and the treatment liquid for generating bubble. A pressure upon bubbling is used to perform ejection of the inks and the treatment liquid. For each head, 64 ejection openings are arranged at a density of 360 dpi. These 64 ejection openings are arranged in alignment in the same direction as the feeding direction of the printing paper 103, namely in substantially perpendicular direction to scanning direction of each head. In the embodiment, ejection amount per each ejection opening is set at 23 pl.

[0203] A distance between each individual head is ½ in. Accordingly, the distance between the heads 101Bk and 101S becomes 1 inch. Since a printing density in the scanning direction is 720 dpi and ejection frequency of each head is 7.2 KHz, a period from ejection of the pigment ink of the head 101Bk to ejection of the treatment liquid of the head 101S becomes 0.05 sec.

[0204]FIGS. 12A to 12C are diagrammatic illustration showing ejection opening arrays of other examples of a head construction in the serial printing apparatus shown in FIG. 11.

[0205] As shown in FIG. 12A, the head may be constructed to have two ejection portions (ejection portions 101Bk1 and 101Bk2) for ejecting black ink as the mixed ink, and the ejection portion 101S ejecting the treatment liquid is arranged therebetween. In this case, after application of the mixed ink of black, the treatment liquid is applied, and subsequently the mixed ink of black is further applied.

[0206] The head construction shown in FIGS. 12B and 12C as well as FIG. 12A, is constructed, in which the head constructions for several inks or treatment liquid are integrated. Of course, in these head unit of integral construction, the ejection openings per the inks or the treatment liquid or liquid chambers and so forth communicated thereto are mutually separated. Accordingly, each ejection portion is similar to the head of each ink or treatment liquid.

[0207] Similarly to FIG. 12A, FIG. 12B shows an example, in which two ejection openings ejecting black ink of the mixed ink. However, this embodiment, the ejection portions 101Bk1 and 101BK2 for the mixed ink and the ejection portion for the treatment liquid are arranged so that the mixed ink is ejected through two ejection portions 101Bk1 and 101Bk2 in advance of ejection of the treatment liquid. With such construction, after deposition of two droplets of black ink of the mixed ink, the treatment liquid is applied.

[0208]FIG. 12C shows an example which is similar in arrangement and number to the embodiment shown in FIG. 11 in terms of arrangement and number of ejection portion 101Bk ejecting the mixed ink of the black ink and the ejection portion 101S ejecting the treatment liquid, and is differentiated in constructions of the ejection portions of respective of C, M and Y inks. Respective two ejection portions of respective of C, M, Y inks (ejection portions 101C1, 101C2, ejection openings 101M1, 101M2 and ejection portions 101Y1, 101Y2) are provided. The ejection portions 101C1, 101M1 and 101Y1 and ejection portions 101C2, 101M2 and 101Y2 are respectively arranged in the direction perpendicular to the scanning direction, per each ink. In this head construction, a plurality of times of scanning with feeding of the printing paper between each scan is effected for overlaying respective inks of C, M and Y. Two ejection portions of each ink, respectively eject high density and low density inks.

[0209] As shown in FIGS. 12A and 12B, when two ejection portions of the mixed ink of black ink are present, for example, content of no dispersant pigment and the dye in the mixed ink to be ejected from respective ejection portions are the same in either ejection openings. However, the contents of no dispersant pigment and the dye in the mixed ink to be ejected from respective ejection portions may be differentiated. For example, a ratio of the pigment and the dye may be 3:7 in the ejection portion 101Bk1 and 7:3 in the ejection portion 101Bk2. Conversely, the ratio may be 7:3 in the ejection portion 101Bk1 and 3:7 in the ejection portion 101Bk2.

[0210] (Third Embodiment)

[0211] In further embodiment of the present invention, as shown in FIG. 12A, the printing head or ejection portion are arranged. Namely, in FIG. 12A, the mixed ink of black is ejected from ejection portions 101Bk1 and 101Bk2, and the treatment liquid is ejected from the ejection portion 101S. Then, the mixed ink, the treatment liquid and the mixed ink are ejected in sequential order.

[0212] In this embodiment, in each ejection portion, the ejection openings are arranged at a density of 600 dpi. The ejection amount of each ejection opening is 15 pl. An interval between the ejection portions is ½ inch similarly to the foregoing second embodiment. The ejection frequency is 10 KHz, and the resolution in printing is 600 dpi in both of the auxiliary scanning direction (paper feeding direction) and primary scanning direction (head scanning direction). Therefore, interval of ejection of the mixed ink and the treatment liquid becomes 30 msec. The treatment liquid contains 0.7% of acetylenol to have high penetrative property.

[0213] According to the construction of the embodiment, the OD value of printing of black character or the like as high as 1.5 or higher, can be obtained. Also, fluidizing of the reaction product by the treatment liquid is little, “overflow” or feathering can also be prevented successfully. Since high penetrative type treatment liquid is used, relatively high fixing ability can be achieved.

[0214] (Fourth Embodiment)

[0215] In the shown embodiment, the construction of the embodiment illustrated in FIGS. 7 and 8 is applied for the mode, in which the pigment ink and the dye ink are ejected individually instead of ejecting the mixed ink. In this case, respective of the head 101Bk1 for the pigment ink of black, the head 101Bk2 for the dye ink of black, the head 101S for the treatment liquid ejecting the treatment liquid, heads for color inks (cyan head 101C, magenta head 101M and yellow head 101Y) among printing heads of the printing head group 101 g are arranged as shown along the feeding direction A of the printing paper 103. Then, by ejecting respective colors of inks and the treatment liquid through respective printing heads, printing of black characters or color image is possible.

[0216] In this embodiment, the pigment ink and the dye ink of black to be ejected through the heads 101Bk1 and 101Bk2 respectively, are low penetrative inks having low penetration speed, and the treatment liquid and cyan, magenta and yellow inks to be ejected through the heads 101S, 101C, 101M and 101Y, respectively are high penetrative inks having high penetration speed.

[0217] Among compositions of the inks to be used in this embodiment, compositions of the inks different from the former embodiment is as follows: [Dye Ink of Black (Bk)] food black 2   4 Wt. % glycerin 7.5 Wt. % diethylene glycol 7.5 Wt. % urea 7.5 Wt. % water remainder [Pigment Ink of Black (Bk)] pigment dispersion liquid  50 Wt. % glycerin   7 Wt. % triethylene glycol   7 Wt. % acetylenol EH 0.2 Wt. % (made by Kawaken Fine Chemical) water remainder

[0218] In the shown embodiment, the pigment ink using no dispersant, no dispersant pigment ink, is used. In this ink, as an anionic carbon black dispersion element, self dispersion type carbon black dispersion element, in which at least one kind of hydrophilic radical is coupled on the surface of the carbon black dispersion element via other atom group, is preferred to use. As the self dispersion type carbon black, the carbon black having ionicity, preferably one charged to have anionic property is preferred.

[0219] By using the pigment and dye inks of black in the embodiment, for a liquid state, in which carbon black particle and black dye charged into the same polarity are mixed and dispersed, the treatment liquid having high molecular of different polarity is reacted.

[0220] In this embodiment, a distance D_(i) (see FIG. 7) between the head 101Bk1 of the pigment ink and the head 101S of the treatment liquid, is 80 mm. Accordingly, a period from ejection of the pigment ink of black to ejection of the treatment liquid is about 0.48 sec. It should be noted that the ejection amount of the printing head is 15 pl per one ejection.

[0221] Next, effect relating to printing quality or so on upon performing printing for a predetermined image of black by the embodiment and result of comparison will be explained using following tables 4 and 5. TABLE 4 Evaluation Comparative Comparative Item System Embodiment Example 1 Example 2 OD Average OD 1.45 1.40 1.37 Value Value of Among Six Printing Papers Minimum OD 1.41 1.29 1.34 Value of Among Six Printing Papers Effective Timing of Water Immediately Within Immediately Resistance After 48 Hours After Printing Printing Fixing Ability Within About About (Minimum Among Six 10 Sec. 80 Sec. 90 Sec. Printing Papers)

[0222] As can be clear from the table 4, in the system of the embodiment, OD value and fixing ability are particularly superior. TABLE 5 Shown Comparative Comparative Embodiment Example 3 Example 4 Evaluation (Mix) + (Pigment) + (Dye) + Item System (Mix) (Pigment) (Dye) OD Average OD 1.45 1.40 1.38 Value Value of Six Printing Papers Minimum OD 1.41 1.37 1.34 Value of Six Printing Papers Fixing Ability ◯ ◯ ◯ Restric- Period of Bk → S ◯ X X tion of 0.48 sec. Feathering Period of Bk → S ◯ X X (Blur or  1.9 sec. the like) Sharpness Period of Bk → S ◯ X X of Edge of 0.48 sec. Solid Period of Bk → S ◯ X X Printing  1.9 sec.

[0223] From this table, it can be appreciated that the embodiment is particularly superior in the OD value. Namely, concerning this OD value, when the treatment liquid is applied to the mixture of the pigment ink and the dye ink such as this embodiment, the foregoing effect is caused by mixing to achieve higher OD value than the case where the treatment liquid is applied to only pigment ink or only dye ink.

[0224] (Fifth Embodiment)

[0225]FIG. 13 is a general perspective view showing the fifth embodiment of the serial type printing apparatus according to the present invention. It is clear that the printer, in which the treatment liquid is reacted after mixing the dye ink and the pigment ink on the printing medium, is applicable not only for the foregoing full-line type, but also for the serial type printing apparatus. Similar elements to those illustrated in FIG. 7 will be identified by like reference numerals to neglect detailed description thereof in order to avoid redundant disclosure to keep the disclosure simple enough to facilitate clear understanding of the present invention.

[0226] The printing paper 103 as the printing medium is inserted from the paper feeding portion 105 and discharged through the printing portion 126. In this embodiment, generally widely used inexpensive plain paper is used as the printing paper 103. In the printing portion 126, the carriage 107 is constructed to mount the printing heads 101Bk1, 101Bk2, 101S, 101C, 101M and 101Y and to move reciprocally along the guide rail 109 by a driving force of the not shown motor. The printing head 101Bk1 ejects the pigment ink of black, and the printing head 101Bk2 ejects the dye ink of black. The printing heads 101S, 101C, 101M and 101Y respectively eject the treatment liquid, cyan ink, magenta ink and yellow ink, are driven for ejecting the ink and the treatment liquid in the foregoing order. The pigment ink of black is no dispersant ink even in the embodiment.

[0227] To respective heads, the inks and the treatment liquid are supplied from the ink tanks 108Bk1, 108Bk2, 108S, 108C, 108M and 108Y. Upon ink ejection, drive signals are supplied to electrothermal transducers, namely heaters, provided for respective of the ejection openings of respective heads to thereby apply thermal energy to the ink and the treatment liquid for generating bubble. A pressure upon bubbling is used to perform ejection of the inks and the treatment liquid. For each head, 64 ejection openings are arranged at a density of 360 dpi. These 64 ejection openings are arranged in alignment in the same direction as the transporting direction Y of the printing paper 103, namely in substantially perpendicular direction to scanning direction of each head. In the embodiment, ejection amount per each ejection opening is set at 23 pl.

[0228] A distance between each individual head is ½ in. Accordingly, the distance between the heads 101Bk and 101S becomes 1 inch. Since a printing density in the scanning direction is 720 dpi and ejection frequency of each head is 7.2 KHz, a period from ejection of the pigment ink of the head 101 Bk to ejection of the treatment liquid of the head 101S becomes 0.1 sec.

[0229] (Sixth Embodiment)

[0230] In a yet further embodiment of the present invention, in the serial type ink-jet printing apparatus shown in FIG. 13, order of arrangement of the printing heads is modified, and associating with this, order of application of the dye ink and pigment ink of black and the treatment liquid is modified.

[0231] Namely, in FIG. 13, arrangement order of the printing heads is modified in order of the head 101Bk1 and head 101Bk2 (other heads are the same as those of the fifth embodiment). Therefore, the pigment ink of black, the treatment liquid, the dye ink of black are ejected on the printing medium in order. The distance between the heads and ejection frequency of respective head are similar to the second embodiment.

[0232] According to this embodiment, fluidization of the reaction product of the ink and the treatment liquid can be restricted in comparison with the case where the treatment liquid is applied after application of the pigment ink and the dye ink. Therefore, occurrence of “overflow” and “sweep” can be successfully suppressed.

[0233] In the shown embodiment, the self dispersion type pigment ink is used for the pigment ink. While the pigment ink of black is ejected from the head 101Bk1 and the dye ink of black is ejected from the head 101Bk2 in the foregoing explanation, it is also possible to eject the dye ink of black from the head 101Bk1, and the pigment ink of black from the head 101Bk2. Even with the later construction, the equivalent effect to that achieved by the former can be achieved. Even when an interval from ejection of the black ink Bk to ejection of the treatment liquid S is set at 0.1 seconds, substantially similar result of evaluation could be obtained.

[0234] Here, furthermore, detailed explanation of the phenomenon and prediction concerning the mechanism concerning this case are performed. At first, there is a preferred relationship between a ratio of (self-dispersion type) pigment and dye in the ink and a ratio of cationic high polymer PAA (polyaryl amine) and cationic surface active agent G50 (Benzelkonium chloride) in the treatment liquid.

[0235] Namely, while the treatment liquid is set to contain 4% of PAA and 0.5% of G50 (ratio of PAA is about 90%) in the shown embodiment, by varying the ratio of the pigment and dye in the ink as shown in FIGS. 14A to 14C, a result where OD value, striking through property, edge sharpness become maximum, can be obtained in the vicinity of 50%. However, according to increase of ratio of G50 in the treatment liquid, the optical value (peak) of the quality is shifted toward greater ratio of the pigment. Conversely, making the ratio of PAA closer to 100%, the peak is shifted toward greater ratio of the dye. However, the peak of the OD value is not shifted significantly.

[0236] The foregoing phenomenon may be explained by the following reason (predicated mechanism).

[0237] As a model, the self-dispersion type pigment is in a form as illustrated in FIG. 15A. Namely, the pigment is in a burr-like having a large number of fibrous polar group (anionic radical) on the periphery of pigment. PAA as cationic high polymer is a corded substance having a plurality of cationic radical in one molecule as shown in FIG. 15D. When self-dispersion type pigment and PAA are mixed, high polymer of PAA may wreathe around the periphery of self-dispersion type pigment as shown in FIG. 16. However, since cationic PAA is not possible to be coupled with anionic radical of all pigment geometrically, the coupled substance as a whole is in a condition having cationic property as shown in FIG. 16.

[0238] Accordingly, reaction product generated by fine particle pigment and PAA has small intermolecular force to cause electrical repelling to difficult to aggregate into large block. As a result, when dye is not contained, these fine substance may appear as bleeding in smoke form on the periphery of dot.

[0239] However, when dye (FIG. 15B) and pigment are present in the ink in admixing manner, PAA and dye are coupled to be gel form to serve as a kind binder for binding between pigments (see FIG. 17). However, when ratio of pigment versus dye becomes large, fine pigment, even a part, tends to be smoke form to degrade sharpness of the edge. Here, when G50 as cationic surface active agent is contained in the ink in addition to PAA, the G50 (FIG. 15C) may serve to aggregate fine pigment particles, and in conjunction therewith to perform buffering function in reaction of dye and PAA promoting gelation to capture fine particle (see FIG. 18).

[0240] In FIGS. 16 to 18, reaction mode at a boundary portion between two pigments is preliminary shown. However, reaction mode at another portion is not shown because it is complicated.

[0241] Thus, when PAA is bound with dye, bound substance becomes stable in energy. When G50 is bound with self-dispersion type pigment, stability in energy is also established. Namely, mode of reaction may have a kind of selectivity.

[0242] Therefore, when the ratio of G50 in the treatment liquid becomes large, the optimal value of the quality is shifted toward greater ratio of pigment. Conversely, when the ratio of PAA becomes large, the optimal value of the quality is shifted toward greater ratio of dye.

[0243] Here, when the ratio of PAA is high, in order to improve possibility of causing strike through and edge sharpness, the dye may be increased to restrict flow ability of fine pigment particle. However, the reaction product generated by reaction of PAA and only dye, is small in size. Therefore, when penetration ability of the treatment liquid is increased for improving fixing ability, dye may penetrate into the paper in depth direction to make it impossible to obtain high OD value. Therefore, pigment is required. It should be appreciated that presence of the self-dispersion type pigment and dye as coloring material in the ink and presence of high molecular insolubilizing agent in the treatment liquid for making the coloring material in the ink are preferred without presence of pigment basically, even if penetration ability of the treatment liquid is not increased.

[0244] The present invention has been described in detail with respect to the preferred embodiments, and it will now be apparent from the foregoing to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and it is the intention, therefore, in the appended claims to cover all such changes and modifications as fall within the true spirit of the invention. 

What is claimed is:
 1. An ink-jet printing apparatus, in which after application of an ink containing a coloring material onto a printing medium, a treatment liquid making said coloring material of said ink insoluble is applied, said ink being a mixed ink, in which a self dispersion type pigment and a dye are mixed, comprising: application means for separately applying said mixed ink and said treatment liquid onto said printing medium, for mixing said mixed ink and said treatment liquid in a liquid state on said printing medium.
 2. An ink-jet printing apparatus, in which after application of an ink containing a coloring material onto a printing medium, a treatment liquid making said coloring material of said ink insoluble is applied, said ink being a mixed ink, in which a self dispersion type pigment and a dye are mixed, comprising: application means for separately applying said mixed ink and said treatment liquid onto said printing medium, for mixing said mixed ink and said treatment liquid in a liquid state on said printing medium, and for mixture of said mixed ink and said treatment liquid, a mixed ink, in which said self dispersion type pigment and the dye are mixed, being further applied on said printing medium in liquid state.
 3. An ink-jet printing apparatus employing an ink ejecting portion ejecting an ink and a treatment liquid ejecting portion ejecting a treatment liquid making an ink ejected from said ink ejecting portion insoluble and performing printing by ejecting said treatment liquid after ejection of said ink toward a printing medium, said ink ejecting portion being constituted of at least one mixed ink ejecting portion for ejecting a mixed ink, in which a self dispersion type pigment and dye are mixed, comprising: ejecting portion arranging means for arranging said mixed ink ejecting portion and said treatment liquid ejecting portion in a predetermined positional relationship; and control means for relatively moving respective ejecting portions arranged in said arranging means and said printing medium, ejecting said mixed ink and said treatment liquid from respective ejecting portions and mixing said mixed ink and said treatment liquid on said printing medium.
 4. An ink-jet printing apparatus as claimed in any one of claims 1 to 3, wherein said pigment is a pigment, in which at least one kind of anionic radical is coupled on the surface of said pigment directly or through other atom group.
 5. An ink-jet printing apparatus as claimed in claim 4, wherein said anionic radical is at least one kind selected among anionic radicals consisted of —COOM, —SO₃M, —PO₃HM, —PO₃M₂, —SO₂NH₂, —SO₂NHCOR wherein M represents one of hydrogen atom, alkali metal, ammonium and organic ammonium, R represents alkyl radical having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl radical which may have substituent group.
 6. An ink-jet printing apparatus as claimed in claim 4, wherein atom group is alkyl radical having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl radical which may have substituent group.
 7. An ink-jet printing apparatus as claimed in claim 4, wherein more than or equal to 80% of particle of said pigment is grain diameter of 0.05 to 0.3 μm.
 8. An ink-jet printing apparatus as claimed in claim 4, wherein more than or equal to 80% of particle of said pigment is grain diameter of 0.1 to 0.25 μm.
 9. An ink-jet printing apparatus as claimed in claim 8, wherein said mixed ink is black ink.
 10. An ink-jet printing apparatus as claimed in claim 3, wherein said arranging means arranges said mixed ink ejecting portion and said treatment liquid ejecting portion in sequential order in a predetermined direction, and said control means ejects said mixed ink and said treatment liquid onto said printing medium in sequential order for sequentially mixing.
 11. An ink-jet printing apparatus as claimed in claim 3, wherein said arranging means arranges said mixed ink ejecting portion, said treatment liquid ejecting portion and said mixed ink ejecting portion in sequential order in a predetermined direction, and said control means ejects said mixed ink, said treatment liquid and said mixed ink onto said printing medium in sequential order for sequentially mixing.
 12. An ink-jet printing apparatus as claimed in claim 3, wherein said arranging means further arranges a cyan ink ejecting portion ejecting a cyan ink, a magenta ink ejecting portion ejecting a magenta ink and an yellow ink ejecting portion ejecting an yellow ink, following to arrangement positions of said mixed ink ejecting portion and said treatment liquid ejecting portion.
 13. An ink-jet printing apparatus as claimed in claim 12, wherein said treatment liquid has a penetration speed greater than or equal to 5.0 (ml/m²·msec^(1/2)) of Ka value by Bristow method.
 14. An ink-jet printing apparatus as claimed in claim 4, wherein said mixed ink ejecting portion and said treatment liquid ejecting portion are arranged ink ejection openings and treatment liquid ejecting openings within a range corresponding to an entire width of a printing region in said printing medium moved relatively.
 15. An ink-jet printing apparatus as claimed in claim 4, which further comprises driving means for moving said mixed ink ejecting portion and said treatment liquid ejecting portion relative to said printing medium with maintaining positional relationship by said arranging means, and said control means causes said relative movement by scanning of respective ejecting portions relative to said printing medium by controlling said driving means.
 16. An ink-jet printing apparatus as claimed in claim 4, wherein said mixed ink ejecting portion and said treatment liquid ejecting portion generate bubble in said mixed ink and said treatment liquid using a thermal energy and eject said mixed ink and said treatment liquid by pressure of said bubble, respectively.
 17. An ink-jet printing apparatus as claimed in claim 13, wherein said treatment liquid has a penetration speed lower than or 1.0 (ml/m²·msec^(1/2)) of Ka value by Bristow method.
 18. A printing method performing printing by applying a mixed ink, in which a self dispersion type pigment and a dye are mixed, onto a printing medium, and thereafter applying a treatment liquid making said self dispersion type pigment and said dye in said mixed ink insoluble, comprising: step of mixing at least said mixed ink and said treatment liquid by applying said mixed ink and said treatment liquid onto said printing medium.
 19. A printing method performing printing by applying an ink containing a coloring material, and thereafter applying a treatment liquid making said coloring material in said ink insoluble, and said ink being a mixed ink, in which a self dispersion type pigment and a dye are mixed, comprising: step of separately applying said mixed ink and said treatment liquid onto said printing medium, mixing said mixed ink and said treatment liquid on said printing medium in liquid state, and, for a mixture of said mixed ink and said treatment liquid, a mixed ink, in which the self dispersion type pigment and dye are mixed, is mixed on said printing medium in liquid state.
 20. A printing method as claimed in claim 18 or 19, wherein said treatment liquid has a penetration speed greater than or equal to 5.0 (ml/m²·msec^(1/2)) of Ka value by Bristow method.
 21. A printing method for performing printing by applying first and second liquids onto a printing medium, comprising step applying said first and second liquid in overlaying manner in sequential order, penetration speeds of said first and second liquids relative to said printing medium being v₁<v₂ assuming that the penetration speed of said first liquid is v₁ and the penetration speed of said second liquid is v₂.
 22. A method for reducing a coloring material absent region to be caused in a coloring material applying region upon performing printing by forming dot on a printing medium using an ink containing pigment using no dispersant and a treatment liquid making said ink insoluble, wherein said ink contains a dye.
 23. An ink-jet printing method applying a first ink containing a coloring material to a printing medium, applying a treatment liquid for making the coloring material in said first ink insoluble and applying a second ink containing a coloring material, wherein the coloring material of one of said first and second inks is a mixed coloring material, in which a self dispersion type pigment and a dye are mixed, and the coloring material of the other of said first and second inks is a pigment or a dye, said method includes a step of mixing said treatment liquid with said first ink on the surface of said printing medium in liquid state, and mixing said second ink with at least said treatment liquid on the surface of said printing medium in liquid state.
 24. An ink-jet printing apparatus applying a first ink containing a coloring material to a printing medium, applying a treatment liquid for making the coloring material in said first ink insoluble and applying a second ink containing a coloring material, wherein the coloring material of one of said first and second inks is a mixed coloring material, in which a self dispersion type pigment and a dye are mixed, and the coloring material of the other of said first and second inks is a pigment or a dye, and said apparatus comprising applying means for mixing said treatment liquid with said first ink on the surface of said printing medium in liquid state, and mixing said second ink with at least said treatment liquid on the surface of said printing medium in liquid state.
 25. An ink-jet printing apparatus applying a first ink containing a coloring material to a printing medium, applying a treatment liquid for making the coloring material in said first ink insoluble and applying a second ink containing a coloring material, wherein said ink includes a pigment ink primarily containing a pigment as the coloring material and a dye ink primarily containing a dye as the coloring material, said apparatus comprising applying means for separately applying said pigment ink, said dye ink and said treatment liquid, and, on said printing medium, said pigment ink and said dye ink being mixed with said treatment liquid in liquid state, respectively.
 26. An ink-jet printing apparatus applying one of a pigment ink containing a pigment as primary coloring material and a dye ink containing a dye as primary coloring material on a printing medium, thereafter applying a treatment liquid making the coloring material in said ink insoluble, and subsequently applying the other of said pigment ink and said dye ink onto said printing medium, comprising: applying means for separately applying said pigment ink, said dye ink and said treatment liquid, and, on said printing medium, said pigment ink and said dye ink being mixed with said treatment liquid in liquid state respectively.
 27. An ink-jet printing apparatus having an ink ejecting portion ejecting an ink containing a coloring material and a treatment liquid ejecting portion ejecting a treatment liquid making a coloring material in the ink insoluble for performing printing by ejecting said treatment liquid after ejecting the ink toward a printing medium, said ink ejecting portion including a dye ejecting portion ejecting a dye ink primarily containing a dye as a coloring material and a pigment ejecting portion ejecting a pigment ink primarily containing a pigment as a coloring material, comprising: ejecting portion arranging means for arranging said dye ink ejecting portion, said pigment ink ejecting portion and said treatment liquid ejecting portion in a predetermined positional relationship; and control means for relatively moving said ejecting portions arranged by said arranging means and said printing medium, ejecting said pigment ink, said dye ink and said treatment liquid from said ejecting portions, and mixing said pigment ink, said dye ink and said treatment liquid on said printing medium in liquid state.
 28. An ink-jet printing apparatus as claimed in any one of claims 25 to 27, wherein said pigment ink is a self dispersion type pigment ink.
 29. An ink-jet printing apparatus as claimed in claim 28, wherein the pigment in said self dispersion type pigment ink is coupled with at least one kind of anionic radical on the surface directly or through other atom group.
 30. An ink-jet printing apparatus as claimed in claim 29, wherein said anionic radical is at least one kind selected among anionic radicals consisted of —COOM, —SO₃M, —PO₃HM, —PO₃M₂, —SO₂NH₂, —SO₂NHCOR wherein M represents one of hydrogen atom, alkali metal, ammonium and organic ammonium, R represents alkyl radical having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl radical which may have substituent group.
 31. An ink-jet printing apparatus as claimed in claim 29, wherein atom group is alkyl radical having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl radical which may have substituent group.
 32. An ink-jet printing apparatus as claimed in claim 29, wherein more than or equal to 80% of particle of said pigment is grain diameter of 0.05 to 0.3 μm.
 33. An ink-jet printing apparatus as claimed in claim 29, wherein more than or equal to 80% of particle of said pigment is grain diameter of 0.1 to 0.25 μm.
 34. An ink-jet printing apparatus as claimed in any one of claims 25 to 27, wherein said pigment ink contains a dispersant dispersing said pigment.
 35. An ink-jet printing apparatus as claimed in claim 25, wherein said pigment ink and said dye ink is black ink.
 36. An ink-jet printing apparatus as claimed in claim 27, wherein said arranging means arranges said pigment ink ejecting portion, said dye ink ejecting portion and said treatment liquid ejecting portion in sequential order in a predetermined direction, and said control means ejects said pigment ink, said dye ink and said treatment liquid onto said printing medium in sequential order for sequentially mixing.
 37. An ink-jet printing apparatus as claimed in claim 27, wherein said arranging means arranges said dye ink ejecting portion, said pigment ink ejecting portion and said treatment liquid ejecting portion in sequential order in a predetermined direction, and said control means ejects said dye ink, said pigment ink and said treatment liquid onto said printing medium in sequential order for sequentially mixing.
 38. An ink-jet printing apparatus as claimed in claim 27, wherein said arranging means arranges said pigment ink ejecting portion, said treatment liquid ejecting portion and said dye ink ejecting portion in sequential order in a predetermined direction, and said control means ejects said pigment ink, said treatment liquid and said dye ink onto said printing medium in sequential order for sequentially mixing.
 39. An ink-jet printing apparatus as claimed in claim 27, wherein said arranging means arranges said dye ink ejecting portion, said treatment liquid ejecting portion and said pigment ink ejecting portion in sequential order in a predetermined direction, and said control means ejects said dye ink, said treatment liquid and said pigment ink onto said printing medium in sequential order for sequentially mixing.
 40. An ink-jet printing apparatus as claimed in claim 27, wherein said arranging means further arranges a cyan ink ejecting portion ejecting a cyan ink, a magenta ink ejecting portion ejecting a magenta ink and an yellow ink ejecting portion ejecting an yellow ink, following to arrangement positions of said pigment ink ejecting portion, said dye ink ejecting portion and said treatment liquid ejecting portion.
 41. An ink-jet printing apparatus as claimed in claims 25, wherein said treatment liquid has a penetration speed greater than or equal to 5.0 (ml/m²·msec^(1/2)) of Ka value by Bristow method.
 42. An ink-jet printing apparatus as claimed in claim 27, wherein said ink ejecting portion and said treatment liquid ejecting portion are arranged ink ejection openings and treatment liquid ejecting openings within a range corresponding to an entire width of a printing region in said printing medium moved relatively.
 43. An ink-jet printing apparatus as claimed in claim 27, which further comprises driving means for moving said ink ejecting portion and said treatment liquid ejecting portion relative to said printing medium with maintaining positional relationship by said arranging means, and said control means causes said relative movement by scanning of respective ejecting portions relative to said printing medium by controlling said driving means.
 44. An ink-jet printing apparatus as claimed in claim 27, wherein said ink ejecting portion and said treatment liquid ejecting portion generate bubble in said ink and said treatment liquid using a thermal energy and eject said ink and said treatment liquid by pressure of said bubble, respectively.
 45. An ink-jet printing apparatus as claimed in claim 41, wherein said treatment liquid has a penetration speed lower than 1.0 (ml/m²·msec^(1/2)) of Ka value by Bristow method.
 46. A printing method performing printing by applying an ink containing a coloring material, and thereafter applying a treatment liquid making said coloring material in said ink insoluble, and said ink including a pigment ink containing a pigment as a primary coloring material and a dye ink containing a dye as primary color agent, comprising: step of separately applying said pigment ink, said dye ink and said treatment liquid onto said printing medium, mixing said pigment ink, said dye ink and said treatment liquid on said printing medium in liquid state, and, at least said pigment ink, said dye ink and said treatment liquid being mixed in liquid state.
 47. A printing method as claimed in claim 22, wherein said treatment liquid has a penetration speed greater than or equal to 5.0 (ml/m²·msec^(1/2)) of Ka value by Bristow method.
 48. A printing method as claimed in claim 46 or 47, wherein said pigment ink, said dye ink and said treatment liquid are applied on said printing medium in sequential order and mixed thereon.
 49. A printing method as claimed in claim 46 or 47, wherein said dye ink, said pigment ink and said treatment liquid are applied on said printing medium in sequential order and mixed thereon.
 50. A printing method as claimed in claim 46 or 47, wherein said pigment ink, said treatment liquid and said dye ink are applied on said printing medium in sequential order and mixed thereon.
 51. A printing method as claimed in claim 46 or 47, wherein said dye ink, said treatment liquid and said pigment ink are applied on said printing medium in sequential order and mixed thereon.
 52. A printing method for performing printing by applying first, second and third liquids onto a printing medium, comprising step applying said first, second and third liquids in overlaying manner in sequential order, penetration speeds of said first, second and third liquids relative to said printing medium being v_(1<v) ₃ and v₂<v₃ assuming that the penetration speed of said first liquid is v₁, the penetration speed of said second liquid is v₂ and the penetration speed of said third liquid is v₃.
 53. A method for reducing a coloring material absent region to be caused in a coloring material applying region upon performing printing by forming dot on a printing medium using a pigment ink containing pigment as a primary coloring material and a treatment liquid making said coloring material in said pigment ink insoluble, wherein a dye ink containing dye as a primary coloring material is used in addition to said pigment ink and said treatment liquid. 